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Gibbs' Phase Rule: Where it all Begins

David Mogk, Montana State University

Introduction
Minerals are the monitors of the physical and chemical conditions under which they
formed. The occurrences of minerals, their parageneses (stable associations), types of
reactions, and compositional variation (e.g. zoned minerals) all provide important
information about geologic history and processes. Of particular importance to
geologists are:

Estimates of pressure and temperature (geothermobarometry)

Estimates of other physico-chemical conditions such as acidity (pH) and
oxidation state (eH)
Partial pressures of gases (e.g. fugacities of H2O, CO2 , etc.)
Partitioning of major and trace elements between phases (e.g. minerals, melts
and/or fluids) to characterize and quantify petrogenetic processes; and
 Use of minerals in geochronology and
thermochronology

Gibbs' Phase Rule provides the theoretical

foundation, based in thermodynamics, for
characterizing the chemical state of a (geologic)
system, and predicting the equilibrium relations
of the phases (minerals, melts, liquids, vapors)
present as a function of physical conditions
such as pressure and temperature. Gibbs' Phase
Rule also allows us to construct phase diagrams
to represent and interpret phase equilibria in
heterogeneous geologic systems. In the
simplest understanding of phase diagrams,
stable phase (mineral) assemblages are
represented as "fields" (see colored areas on the
figure to the right) in "P-T space", and the
boundaries between stable phase assemblages
are defined by lines (or curves) that represent
reactions between the phase assemblages. The reaction curves actually represent the
condition (or the locus of points in P-T space) where ΔGrxn =0; for more information on
this point see Gibbs Free Energy. A solid understanding of Gibbs' Phase Rule is required
to successfully master the applications of heterogeneous phase equilibria presented in
this module.

Definitions
Gibbs Phase Rule is expressed by the simple formulation:

P + F = C + 2, where

P is the number of phases in the system

A phase is any physically separable material in the system. Every unique mineral
is a phase (including polymorphs); igneous melts, liquids (aqueous solutions),
and vapor are also considered unique phases. It is possible to have two or more
phases in the same state of matter (e.g. solid mineral assemblages, immiscible
silicate and sulfide melts, immiscible liquids such as water and hydrocarbons,
etc.) Phases may either be pure compounds or mixtures such as solid or
aqueous solutions--but they must "behave" as a coherent substance with fixed
chemical and physical properties.
C is the minimum number of chemical components required to constitute all the phases
in the system
For historical reasons, geologists normally define components in terms of the
simple oxides (e.g. SiO2, Al2O3, CaO, etc.). If two possible components always
occur in the same proportions in multiple phases in a system, these can be
combined into a single component (remember, we are always trying to define
the minimum number of components required to make all the phases in the
system). Consider the reaction:

CaMg(CO3)2 + 2 SiO2 = CaMgSi2O6 + 2 CO2

Dolomite + 2 Quartz = Diopside + 2 Carbon Dioxide

Normally we would pick the 4 components: CaO, MgO, SiO2, and CO2 based on
the simple oxides. However, because Ca and Mg are in a 1:1 ratio in both
dolomite and diopside (and not present in quartz or carbon dioxide), we can
consider this a ternary system with components: CaMgO2, SiO2, and CO2

In some geologic systems it is convenient to define the components in terms of

end-member compositions (e.g. binary systems such as carbonates, CaCO3 -
MgCO3; alkali feldspars, NaAlSi3O8 - KAlSi3O8, etc.).

In some cases, a given mineral assemblage may be represented by a sub-set of

the whole system if fewer components are needed to define the compositions of
 the observed mineral assemblage--this is known as a degenerate system. A
good example of this can be seen on a ternary (3 component) chemographic
projection if the phases of interest plot in a co-linear fashion (i.e. requiring only
two components to define the phase compositions in what is otherwise a three
component system).

A more complete discussion of components can be found in the section on

Plotting Mineral Compositions and Chemographic Projections.
F is the number of degrees of freedom in the system (also referred to as the variance of
the system).
For geologic applications, this generally refers to the number of variables (e.g.
pressure and temperature) that can be independently changed without altering
the state of the system (i.e. the number of phases and their compositions are
constant). Three common types of equilibria are possible:

Invariant equilibria, in which neither P or T can be changed; on a phase

diagram, this is represented as a singular invariant point
Univariant equilibria, in which either P or T can be changed
independently, but to maintain the state of the system, there must be a
corresponding change in the other variable; on a phase diagram this is
referred to as a univariant curve
and
 Divariant equilibria, in which both P and T are free to change
independently without changing the state of the system (but bounded by
the conditions defined by the univariant equilibria).

The integer in the Gibbs Phase Rule

is related to the number of intensive parameters (i.e. those that are independent
of mass; such as pressure and temperature) that are being considered. Note
that many phase diagrams consider only one intensive parameter (e.g. T-Xfluid,
where T is intensive, and the mole fraction of fluid is related to the amount of
mass of the fluid components); in this case, the Gibbs Phase Rule would be: P +
F = C + 1.

It is generally the case that as the number of components increase, the variance of the
system must also increase. Conversely, as the number of phases increase in the
system, the variance of the system must correspondingly decrease. A corollary to Gibbs'
Phase Rule is Goldschmidt's Mineralogical Phase Rule: for a given rock in equilibrium at
a fixed P and T, the number of phases is less than or equal to the number of
components. Geologic systems are really rather simple! This means that we have a
reasonable expectation that we can successfully interpret the conditions of formation
of rocks in their natural settings, and to model their behavior using the thermodynamic
databases and programs presented at the end of this module.
Some Simple One-Component Examples
Let's consider the simple 1 component system for H2O:

The system is
entirely
composed of
H2O, so there is
only one
component
present.
The phases Phase diagram for the one component system H2O. This
present diagram is not to scale; a scale version looks like the
represent three thumbnail in the white box.
states of matter:
liquid (water), solid (ice), and vapor (steam). All have distinct physical properties
(e.g. density, structure--or lack of, etc.) and chemical properties (e.g. ΔGformation,
molar volume etc.) so they must be considered distinct phases.
Note that there is only one point on this diagram where all three phases coexist
in equilibrium--this "triple point" is also referred to as an invariant point; because
P and T are uniquely specified, there are zero degrees of freedom.
Each of the curves represents a chemical reaction that describes a phase
transformation: solid to liquid (melt/crystallization), liquid to vapor
(boiling/condensation), solid to vapor (sublimation/deposition). There are three
univariant curves around the invariant point; it is always the case that for a C-
component system, there will always be C+2 univariant curves radiating around
an invariant point. This relationship is further explained in the unit on the Method
of Schreinemakers. There is only one degree of freedom along each of the
univariant curves: you can independently change either T or P, but to maintain
two coexisting phases along the curve the second variable must change by a
corresponding fixed amount.
There are three distinct areas where only ice, liquid, or vapor exit. These are
divariant fields. T and P are both free to change within these fields and you will
 still have only one phase (a bit hotter or colder, or compressed or expanded, but
nonetheless the same phase).
The end of the "boiling curve", separating the liquid to vapor transition, is called
the "critical point". This is a particularly interesting part of the phase diagram
because beyond this region the physico-chemical properties of water and steam
converge to the point where they are identical. Thus, beyond the critical point, we
refer to this single phase as a "supercritical fluid".

Now, let's consider a simple 1 component system that describes the mineral phases in
the aluminosilicate system:

The entire system is defined by one component: Al2SiO5 (i.e. all the phases can
be completely made of this one component)
There are three solid phases shown in this diagram: the polymorphs of Al2SiO5
andalusite, kyanite and sillimanite.
There is only one unique place on this diagram where all three phases can
coexist in equilibrium--the invariant point at 3.8 Kb and 500oC; at this point there
are zero degrees of freedom.
Phase diagram for the one component system Al2SiO5.
 There are three univariant reactions on this diagram, each representing the
phase transitions: andalusite = sillimanite, andalusite = kyanite, and kyanite =
sillimanite. In each of these reactions, either pressure or temperature can be
changed independently, but for the state of the system to remain the same (i.e.
two solid phases coexisting in equilibrium), the other variable must change by a
fixed amount to maintain the assemblage on the univariant curve -- so there is
one degree of freedom. In a later section, we will see that the univariant curves
represent the condition where ΔGrxn = 0 (i.e. the intersection of the "free energy
surface" with the Pressure-Temperature plane represented by the phase
diagram).
There are three divariant fields in which only a single mineral phase is stable.
Within these fields pressure and temperature may be changed independently
without changing the state of the system--thus there are two degrees of freedom
in the divariant fields.

These principles extend to the more complicated binary, ternary and multi-component
systems presented in the next section(s) of this module on Phase Diagrams and
Pseudosections.

Assumptions
There are a number of important assumptions that must be considered when applying
Gibbs' Phase Rule:

The relationships described by the Gibbs' Phase Rule apply the concepts of
equilibrium thermodynamics. It is assumed that geologic systems have enough
time to naturally equilibrate. It is also assumed that geologic systems are
"closed" systems--that is the mass of the system remains essentially constant,
and the system is free to consume or liberate energy to do work.
For geologic systems, heat and work are considered to be the major contributors
to the system's energetics--that is, "P-V work" is the dominant source of energy
consumed/liberated by the system. We do not consider the effects of external
fields (e.g. electrical, magnetic, gravitational), and we do not consider surface
energy or boundary effects.
No kinetic effects are considered. This may present problems with an
equilibrium thermodynamics approach if metastable phases are present in the
system. In natural settings it is common for a given mineral to exist under
physical conditions that exceed its predicted stability limits. A good example is
the persistence of kyanite into the sillimanite stability field. This particular
reaction a) has a very small ΔGrxn (and thus, a small "driving force" to make the
reaction go), and b) the polymorphic reaction is of the "reconstructive" kind, and
requires the breaking and reforming of strong covalent bonds. The presence of
metastable phases may complicate matters in trying to determine the
equilibrium conditions for stable mineral assemblages, but they are essential
indicators of changing physical conditions that allow us to interpret Pressure-
Temeperature-time Paths.
In some cases, surface reactions (e.g. sorption, catalysis) may operate in
geological environment and contribute to the overall energetics of the system.
Surface energies are not included in the Gibbs Phase Rule formulation.
Gibbs' Phase Rule cannot be applied indiscriminately. It is important to obtain
the best possible characterization of the identity, composition and structural
state of the phases present. For example, complex materials such as mixed
layer silicates may cause problems, or minerals that exhibit a range of structural
states (e.g. the alkali feldspars). An overview of analytical techniques that are
used to characterize minerals, melts and fluids can be found at the companion
website on Geochemical Instrumentation and Analysis
Recognizing these assumptions and limitations, the Gibbs Phase Rule still
provides a powerful way to analyze and interpret geological systems. Although
geologic systems are dynamic and often in a state of disequilibrium, the
equilibrium approach demonstrates what the state of the system would be given
sufficient time and energy to achieve that equilibrium. It also provides
information on the phase changes or reactions that would be expected in a
system that is thrown out of equilibrium due to changes in physical conditions.
Thus a knowledge of the sequence of possible reactions provides important
information about "pathways" in geologic systems that allow interpretations of
 tectonic environments, petrogenetic processes, and the evolution of geologic
systems (see following chapters on Pseudosections, P-T-t Paths, and Advanced
Modeling Programs (ThermoCalc, TWEEQ, PERPLEX, MELTS).

Derivation of the Phase Rule

It is important to recognize that the simple formulation of Gibbs' Phase Rule is
derivative from fundamental thermodynamic principles. The Gibbs- Duhem equation
establishes the relationship between the intensive parameters temperature (T) and
pressure (P) and the chemical potential of all components (μi) in the system:
dG = Vdp - Sdt + ΣNidμi
This means that there are

C + 2 independent variables that describe the system: P, T and one each for the
chemical potential for all components, and
P independent equations (of the Gibbs-Duhem form) that describe the
energetics of the system--one equation for each phase.

In mathematical terms, the variance (F) is determined by the difference between (C+2)
variables and (P) equations. Thus,

F = C + 2 - P or as originally written, P + F = C + 2
A more extensive derivation of the phase rule can be found at the website of W. R.
Salzman, Department of Chemistry, University of Arizona or this PowerPoint
presentation on the derivation of the Phase Rule (PowerPoint 337kB Sep18 07) by Marty
Rutstein, SUNY New Paltz.

Problem Sets/Labs/Activities on Simple Phase Diagrams

Problem Set: Phase Diagrams - Dexter Perkins, University of North Dakota; this is
a problem set that introduces students to the basics of simple phase diagrams,
and their relationship to Gibbs' Phase Rule.
Phase Rule and Binary Systems (more info) - John Winter, Whitman College,
PowerPoint (Chapter 6)
PowerPoint presentation on the derivation of the Phase Rule (PowerPoint 337kB
Sep18 07)--Marty Rutstein, SUNY New Paltz,

Examples of the use of Gibbs' Phase Rule in creating and interpreting more complex
phase diagrams are presented in the next section.